Remote hydrogen plasma titanium deposition to enhance selectivity and film uniformity

ABSTRACT

Methods and apparatus to selectively deposit metal films (e.g., titanium films) are described. One of the precursors is energized to form ions and radicals of the precursor. The precursors flow through separate channels of a dual channel gas distribution assembly to react in a processing region above a substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/417,087, filed Nov. 3, 2016, and U.S. Provisional Application No.62/453,113, filed Feb. 1, 2017, the entire disclosures of which arehereby incorporated by reference herein.

TECHNICAL FIELD

The present disclosure relates generally to apparatus and methods fordepositing semiconductor films. In particular, the disclosure relates toapparatus and methods for depositing titanium films with enhancedselectivity and film uniformity.

BACKGROUND

Integrated circuits are made possible by processes which produceintricately patterned material layers on substrate surfaces. Producingpatterned material on a substrate requires controlled methods forremoval of exposed material. Selectively depositing a film on onesurface relative to a different surface is useful for patterning andother applications.

Plasma-Enhanced Chemical Vapor Deposition (PECVD) using direct plasmahas been shown to deposit metal films (e.g., titanium) selectively onsilicon relative to silicon oxide surfaces with selectivity up to 8:1.However, the film deposited is non-uniform due to the uniformity of thedirect plasma distribution.

Therefore, there is a need in the art for apparatus and methods toincrease deposition uniformity for selectively deposited films.

SUMMARY

One or more embodiments of the disclosure are directed to processingmethods comprising flowing a first precursor into a volume in aprocessing chamber. The volume is bounded by a chamber top and a gasdistribution assembly. The first precursor is energized in the volumeand allowed to flow through first fluid channels formed in the gasdistribution assembly into a processing region in the processingchamber. A second precursor is flowed through second fluid channels inthe gas distribution assembly into the processing region to react thefirst precursor in the processing region.

Additional embodiments of the disclosure are directed to processingmethods comprising positioning a substrate with a first surface and asecond surface different from the first surface in a processing regionof a processing chamber. An energized first precursor is flowed througha dual channel gas distribution assembly into the processing region. Asecond precursor is flowed through the dual channel gas distributionassembly into the processing region. The energized first precursor andthe second precursor are reacted in the processing region to deposit afilm on the first surface.

Further embodiments of the disclosure are directed to processing methodscomprising positioning a substrate with a first surface and a secondsurface different from the first surface in a processing region of aprocessing chamber. The first surface comprises silicon and the secondsurface comprises silicon oxide. A first precursor comprising H₂ isenergized to form H⁺ and H* species in a volume and the energized firstprecursor is flowed through first fluid channels in a dual channel gasdistribution assembly into the processing region. A second precursorcomprising titanium chloride is flowed through second fluid channels inthe dual channel gas distribution assembly into the processing region.The second fluid channels are isolated from the first fluid channels.The energized first precursor and the second precursor are reacted inthe processing region to deposit a titanium film selectively on thefirst surface relative to the second surface with a selectivity greaterthan or equal to about 10:1.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this disclosure and are therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective embodiments.

FIG. 1 shows a top plan view of one embodiment of an exemplaryprocessing tool in accordance with one or more embodiment of thedisclosure;

FIG. 2 shows a schematic cross-sectional view of an exemplary processingchamber in accordance with one or more embodiment of the disclosure;

FIGS. 3A-3D show schematic views of exemplary showerhead configurationsaccording to one or more embodiment of the disclosure;

FIG. 4 shows a simplified cross-sectional view of a processing chamberaccording to one or more embodiment of the disclosure;

FIG. 5 shows a flowchart of a method of operation for a semiconductorprocessing chamber according to one or more embodiment of thedisclosure;

FIG. 6 shows a simplified cross-sectional view of a processing chamberaccording to one or more embodiment of the disclosure; and

FIG. 7 shows a schematic representation of a selective depositionprocess in accordance with one or more embodiment of the disclosure.

In the appended figures, similar components and/or features may have thesame reference label. Further, various components of the same type maybe distinguished by following the reference label by a dash and a secondlabel that distinguishes among the similar components. If only the firstreference label is used in the specification, the description isapplicable to any one of the similar components having the same firstreference label irrespective of the second reference label.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the disclosure, it isto be understood that the disclosure is not limited to the details ofconstruction or process steps set forth in the following description.The disclosure is capable of other embodiments and of being practiced orbeing carried out in various ways.

A “substrate” as used herein, refers to any substrate or materialsurface formed on a substrate upon which film processing is performedduring a fabrication process. For example, a substrate surface on whichprocessing can be performed include materials such as silicon, siliconoxide, strained silicon, silicon on insulator (SOI), carbon dopedsilicon oxides, amorphous silicon, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Substrates include, without limitation, semiconductorwafers. Substrates may be exposed to a pretreatment process to polish,etch, reduce, oxidize, hydroxylate, anneal and/or bake the substratesurface. In addition to film processing directly on the surface of thesubstrate itself, in the present disclosure, any of the film processingsteps disclosed may also be performed on an under-layer formed on thesubstrate as disclosed in more detail below, and the term “substratesurface” is intended to include such under-layer as the contextindicates. Thus for example, where a film/layer or partial film/layerhas been deposited onto a substrate surface, the exposed surface of thenewly deposited film/layer becomes the substrate surface.

As used in this specification and the appended claims, the terms“precursor”, “reactant”, “reactive gas” and the like are usedinterchangeably to refer to any gaseous species that can react with thesubstrate surface.

FIG. 1 shows a top plan view of one embodiment of a processing tool 100for deposition, etching, baking, and/or curing according to one or moreembodiments of the disclosure. In the figure, a pair of FOUPs (frontopening unified pods) 102 supply substrates (e.g., specified diametersemiconductor wafers) that may be received by robotic arms 104 andplaced into a low-pressure holding area 106 before being placed into oneof the substrate processing sections 108 a-f of the tandem processchambers 109 a-c. A second robotic arm 110 may be used to transport thesubstrates from the holding area 106 to the processing chambers 108 a-fand back.

The substrate processing sections 108 a-f of the tandem process chambers109 a-c may include one or more system components for depositing,annealing, curing and/or etching substrates or films thereon. Exemplaryfilms may be flowable dielectrics, but many types of films may be formedor processed with the processing tool. In one configuration, two pairsof the tandem processing sections of the processing chamber (e.g., 108c-d and 108 e-f) may be used to deposit the dielectric material on thesubstrate, and the third pair of tandem processing sections (e.g., 108a-b) may be used to anneal the deposited dielectric. In anotherconfiguration, the two pairs of the tandem processing sections ofprocessing chambers (e.g., 108 c-d and 108 e-f) may be configured toboth deposit and anneal a dielectric film on the substrate, while thethird pair of tandem processing sections (e.g., 108 a-b) may be used forUV or E-beam curing of the deposited film. In still anotherconfiguration, all three pairs of tandem processing sections (e.g., 108a-f) may be configured to deposit and cure a dielectric film on thesubstrate or etch features into a deposited film

In yet another configuration, two pairs of tandem processing sections(e.g., 108 c-d and 108 e-f) may be used for both deposition and UV orE-beam curing of the dielectric, while a third pair of tandem processingsections (e.g. 108 a-b) may be used for annealing the dielectric film.In addition, one or more of the tandem processing sections 108 a-f maybe configured as a treatment chamber, and may be a wet or dry treatmentchamber. These process chambers may include heating the dielectric filmin an atmosphere that includes moisture. Thus, embodiments of system 100may include wet treatment tandem processing sections 108 a-b and annealtandem processing sections 108 c-d to perform both wet and dry annealson the deposited dielectric film. It will be appreciated that additionalconfigurations of deposition, etching, annealing, and curing chambersfor dielectric films are contemplated by system 100.

FIG. 2 is a cross-sectional view of an exemplary process chamber section200 with partitioned plasma generation regions within the processingchambers. During film etching (e.g., silicon, polysilicon, siliconoxide, silicon nitride, silicon oxynitride, silicon oxycarbide), aprocess gas may be flowed into the first plasma region 215 through a gasinlet assembly 205. A remote plasma system (RPS) 201 may process a firstgas which then travels through gas inlet assembly 205, and a second RPS202 may process a second gas, which then travels through a side inlet inthe process chamber 200. The inlet assembly 205 may include two distinctgas supply channels where the second channel (not shown) may bypass theRPS 201. In one example, the first channel provided through the RPS maybe used for the process gas and the second channel bypassing the RPS maybe used for a treatment gas in disclosed embodiments. The process gasmay be excited prior to entering the first plasma region 215 within theRPS 201. A cooling plate 203, faceplate 217, showerhead 225, and asubstrate support 265, having a substrate 255 disposed thereon, areshown according to disclosed embodiments. The faceplate 217 may bepyramidal, conical, or of another similar structure with a narrow topportion expanding to a wide bottom portion. The faceplate 217 mayadditionally be flat as shown and include a plurality ofthrough-channels (not shown) used to distribute process gases. Thefaceplate (or conductive top portion) 217 and showerhead 225 are shownwith an insulating ring 220 in between, which allows an AC potential tobe applied to the faceplate 217 relative to showerhead 225. Theinsulating ring 220 may be positioned between the faceplate 217 and theshowerhead 225 enabling a capacitively coupled plasma (CCP) to be formedin the first plasma region. A baffle (not shown) may additionally belocated in the first plasma region 215 to affect the flow of fluid intothe region through gas inlet assembly 205.

Exemplary configurations include having the gas inlet assembly 205 openinto a gas supply region partitioned from the first plasma region 215 byfaceplate 217 so that the gases/species flow through the holes in thefaceplate 217 into the first plasma region 215. Structural andoperational features may be selected to prevent significant backflow ofplasma from the first plasma region 215 back into the supply region, gasinlet assembly 205, and fluid supply system 210. The structural featuresmay include the selection of dimensions and cross-sectional geometry ofthe apertures in faceplate 217 that deactivates back-streaming plasma.The operational features may include maintaining a pressure differencebetween the gas supply region and first plasma region 215 that maintainsa unidirectional flow of plasma through the showerhead 225.

A fluid, such as a precursor, for example a fluorine-containingprecursor, may be flowed into the processing region 233 by embodimentsof the showerhead described herein. Excited species derived from theprocess gas in the plasma region 215 may travel through apertures in theshowerhead 225 and react with an additional precursor flowing into theprocessing region 233 from a separate portion of the showerhead. Littleor no plasma may be present in the processing region 233. Excitedderivatives of the precursors may combine in the region above thesubstrate and, on occasion, on the substrate to etch structures orremove species on the substrate in disclosed applications.

Exciting the fluids in the first plasma region 215 directly, excitingthe fluids in one or both of the RPS units 201, 202, or both, mayprovide several benefits. The concentration of the excited speciesderived from the fluids may be increased within the processing region233 due to the plasma in the first plasma region 215. This increase mayresult from the location of the plasma in the first plasma region 215.The processing region 233 may be located closer to the first plasmaregion 215 than the remote plasma system (RPS) 201, leaving less timefor the excited species to leave excited states through collisions withother gas molecules, walls of the chamber, and surfaces of theshowerhead.

The uniformity of the concentration of the excited species derived fromthe process gas may also be increased within the processing region 233.This may result from the shape of the first plasma region 215, which maybe more similar to the shape of the processing region 233. Excitedspecies created in the RPS 201, 202 may travel greater distances inorder to pass through apertures near the edges of the showerhead 225relative to species that pass through apertures near the center of theshowerhead 225. The greater distance may result in a reduced excitationof the excited species and, for example, may result in a slower growthrate near the edge of a substrate. Exciting the fluids in the firstplasma region 215 may mitigate this variation for the fluid flowedthrough RPS 201.

The processing gases may be excited in the RPS 201, 202 and may bepassed through the showerhead 225 to the processing region 233 in theexcited state. Alternatively, power may be applied to the firstprocessing region to either excite a plasma gas or enhance an alreadyexcited process gas from the RPS. While a plasma may be generated in theprocessing region 233, a plasma may alternatively not be generated inthe processing region. In one example, the only excitation of theprocessing gas or precursors may be from exciting the processing gasesin the RPS units 201, 202 to react with one another in the processingregion 233.

The processing system may further include a power supply 240electrically coupled with the processing chamber to provide electricpower to the faceplate 217 and/or showerhead 225 to generate a plasma inthe first plasma region 215 or processing region 233. The power supplymay be configured to deliver an adjustable amount of power to thechamber depending on the process performed.

In addition to the fluid precursors, there may be other gases introducedat varied times for varied purposes, including carrier gases to aiddelivery. A treatment gas may be introduced to remove unwanted speciesfrom the chamber walls, the substrate, the deposited film and/or thefilm during deposition. A treatment gas may be excited in a plasma andthen used to reduce or remove residual content inside the chamber. Inother disclosed embodiments the treatment gas may be used without aplasma. When the treatment gas includes water vapor, the delivery may beachieved using a mass flow meter (MFM), an injection valve, or bycommercially available water vapor generators. The treatment gas may beintroduced from the first processing region, either through the RPS unitor bypassing the RPS unit, and may further be excited in the firstplasma region.

The gas distribution assemblies 225 for use in the processing chambersection 200 are referred to as dual channel showerheads (DCSH) and aredetailed in the embodiments described in FIGS. 3A-3D herein. The dualchannel showerhead may allow for flowable deposition of a dielectricmaterial, and separation of precursor and processing fluids duringoperation. The showerhead may alternatively be utilized for etchingprocesses that allow for separation of etchants outside of the reactionzone to provide limited interaction with chamber components and eachother prior to being delivered into the processing region.

Referring generally to the showerheads in FIGS. 3A-3D, precursors may beintroduced into the processing region by first being introduced into aninternal showerhead volume 327 defined in the showerhead 300 by a firstmanifold 320, or upper plate, and second manifold 325, or lower plate.The manifolds may be perforated plates that define a plurality ofapertures. The precursors in the internal showerhead volume 327,typically referred to as the second precursors, may flow into theprocessing region 233 via apertures 375 formed in the lower plate. Thisflow path may be isolated from the rest of the process gases in thechamber, and may provide for the precursors to be in an unreacted orsubstantially unreacted state until entry into the processing region 233defined between the substrate 255 and a bottom of the lower plate 325.Alternatively, second RPS 202 may be used to excite or produce radicalspecies of the second precursor. These radical species may be maintainedseparate from the other radical species of the first precursor that mayflow through the first apertures 360. Once in the processing region 233,the two precursors may react with each other and the substrate. Thesecond precursor may be introduced into the internal showerhead volume327 defined in the showerhead 300 through a side channel formed in theshowerhead, such as channel 322 as shown in the showerhead embodimentsherein. The first precursor gas may be in a plasma state includingradicals from the RPS unit or from a plasma generated in the firstplasma region. Additionally, a plasma may be generated in the processingregion.

FIG. 3A illustrates an upper perspective view of a gas distributionassembly 300. In usage, the gas distribution system 300 may have asubstantially horizontal orientation such that an axis of the gasapertures formed therethrough may be perpendicular or substantiallyperpendicular to the plane of the substrate support (see substratesupport 265 in FIG. 2). FIG. 3B illustrates a bottom perspective view ofthe gas distribution assembly 300. FIG. 3C is a bottom plan view of thegas distribution assembly 300. FIG. 3D is a cross sectional views of anexemplary embodiment of gas distribution assembly 300 taken along lineA-A of FIG. 3C.

Referring to FIGS. 3A-3D, the gas distribution assembly 300 generallyincludes the annular body 340, the upper plate 320, and the lower plate325. The annular body 340 may be a ring which has an inner annular wall301 located at an inner diameter, an outer annular wall 305 located atan outer diameter, an upper surface 315, and a lower surface 310. Theupper surface 315 and lower surface 310 define the thickness of theannular body 340. A conduit 350 may be formed in the annular body 340and a cooling fluid may be flowed within the channel that extends aroundthe circumference of the annular body 340. Alternatively, a heatingelement 351 may be extended through the channel that is used to heat theshowerhead assembly.

One or more recesses and/or channels may be formed in or defined by theannular body as shown in disclosed embodiments including thatillustrated in FIG. 3D. The annular body may include an upper recess 303formed in the upper surface, and a first lower recess 302 formed in thelower surface at the inner annular wall 301. The annular body may alsoinclude a second lower recess 304 formed in the lower surface 310 belowand radially outward from the first lower recess 302. As shown in FIG.3D, an inner fluid channel 306 may be defined in the upper surface 315,and may be located in the annular body radially inward of the upperrecess 303. The inner fluid channel 306 may be annular in shape and beformed the entire distance around the annular body 340. In disclosedembodiments, a bottom portion of the upper recess 303 intersects anouter wall of the inner fluid channel 306 (not shown). The inner fluidchannel may also be at least partially radially outward of the secondlower recess 304. A plurality of ports 312 may be defined in an innerwall of the inner fluid channel, also the inner annular wall 301 of theannular body 340. The ports 312 may provide access between the innerfluid channel and the internal volume 327 defined between the upperplate 320 and lower plate 325. The ports may be defined around thecircumference of the channel at specific intervals, and may facilitatefluid distribution across the entire region of the volume 327 definedbetween the upper and lower plates. The intervals of spacing between theports 312 may be constant, or may be varied in different locations toaffect the flow of fluid into the volume. The inner and outer walls,radially, of the inner fluid channel 306 may be of similar or dissimilarheight. For example, the inner wall may be formed higher than the outerwall to affect the distribution of fluids in the inner fluid channel toavoid or substantially avoid the flow of fluid over the inner wall ofthe first fluid channel.

Again referring to FIG. 3D, an outer fluid channel 308 may be defined inthe upper surface 315 that is located in the annular body radiallyoutward of the inner fluid channel 306. Outer fluid channel 308 may bean annular shape and be located radially outward from and concentricwith inner fluid channel 306. The outer fluid channel 308 may also belocated radially outward of the first upper recess 303 such that theouter fluid channel 308 is not covered by the upper plate 320, or may beradially inward of the first upper recess 303 as shown, such that upperplate 320 covers the outer fluid channel 308. A second plurality ofports 314 may be defined in the portion of the annular body 340 definingthe outer wall of the inner fluid channel 306 and the inner wall of theouter fluid channel 308. The second plurality of ports 314 may belocated at intervals of a pre-defined distance around the channel toprovide fluid access to the inner fluid channel 306 at several locationsabout the outer fluid channel 308. In operation, a precursor may beflowed from outside the process chamber to a delivery channel 322located in the side of the annular body 340. This delivery channel 322may be in fluid communication with the second RPS 202 through a secondaccess in the processing chamber. The fluid may flow into the outerfluid channel 308, through the second plurality of ports 314 into theinner fluid channel 306, through the first plurality of ports 312 intothe internal volume 327 defined between the upper and lower plates, andthrough the third apertures 375 located in the bottom plate 325. Assuch, a fluid provided in such a fashion can be isolated orsubstantially isolated from any fluid delivered into the first plasmaregion through apertures 360 until the fluids separately exit the lowerplate 325.

The upper plate 320 may be a disk-shaped body, and may be coupled withthe annular body 340 at the first upper recess 303. The upper plate 320may thus cover the first fluid channel 306 to prevent or substantiallyprevent fluid flow from the top of the first fluid channel 306. Theupper plate may have a diameter selected to mate with the diameter ofthe upper recess 303, and the upper plate may comprise a plurality offirst apertures 360 formed therethrough. The first apertures 360 mayextend beyond a bottom surface of the upper plate 320 thereby forming anumber of raised cylindrical bodies (not shown). In between each raisedcylindrical body may be a gap. As seen in FIG. 3A, the first apertures360 may be arranged in a polygonal pattern on the upper plate 320, suchthat an imaginary line drawn through the centers of the outermost firstapertures 360 define or substantially define a polygonal figure, whichmay be for example, a six-sided polygon.

The lower plate 325 may have a disk-shaped body having a number ofsecond apertures 365 and third apertures 375 formed therethrough, asespecially seen in FIG. 3C. The lower plate 325 may have multiplethicknesses, with the thickness of defined portions greater than thecentral thickness of the upper plate 320, and in disclosed embodimentsat least about twice the thickness of the upper plate 320. The lowerplate 325 may also have a diameter that mates with the diameter of theinner annular wall 301 of the annular body 340 at the first lower recess302. The second apertures 365 may be defined by the lower plate 325 ascylindrical bodies extending up to the upper plate 320. In this way,channels may be formed between the first and second apertures that arefluidly isolated from one another, and may be referred to as first fluidchannels. Additionally, the volume 327 formed between the upper andlower plates may be fluidly isolated from the channels formed betweenthe first and second apertures. As such, a fluid flowing through thefirst apertures 360 will flow through the second apertures 365 and afluid within the internal volume 327 between the plates will flowthrough the third apertures 375, and the fluids will be fluidly isolatedfrom one another until they exit the lower plate 325 through either thesecond or third apertures. Third apertures 375 may be referred to assecond fluid channels, which extend from the internal volume 327 throughthe bottom plate 325. This separation may provide numerous benefitsincluding preventing a radical precursor from contacting a secondprecursor prior to reaching a processing region. By preventing theinteraction of the gases, reactions within the chamber may be minimizedprior to the processing region in which the reaction is desired.

The second apertures 365 may be arranged in a pattern that aligns withthe pattern of the first apertures 360 as described above. In oneembodiment, when the upper plate 320 and bottom plate 325 are positionedone on top of the other, the axes of the first apertures 360 and secondapertures 365 align. In disclosed embodiments, the upper and lowerplates may be coupled with one another or directly bonded together.Under either scenario, the coupling of the plates may occur such thatthe first and second apertures are aligned to form a channel through theupper and lower plates. The plurality of first apertures 360 and theplurality of second apertures 365 may have their respective axesparallel or substantially parallel to each other, for example, theapertures 360, 365 may be concentric. Alternatively, the plurality offirst apertures 360 and the plurality of second apertures 365 may havethe respective axis disposed at an angle from about 1° to about 30° fromone another. At the center of the bottom plate 325 there may or may notbe a second aperture 365.

Referring again to FIG. 3D, a pair of isolation channels, 324 may beformed in the annular body 340. One of the pair of isolation channels324 may be defined in the upper plate 320, and the other of the pair ofisolation channels 324 may be defined in the lower surface 310 of theannular body 340. Alternatively, as shown in FIG. 3A, one of the pair ofisolation channels 324 may be defined in the upper surface 315 of theannular body 340. The pair of isolation channels may be verticallyaligned with one another, and in disclosed embodiments may be in directvertical alignment. Alternatively, the pair of isolation channels may beoffset from vertical alignment in either direction. The channels mayprovide locations for isolation barriers such as o-rings in disclosedembodiments.

Turning to FIG. 4, a simplified schematic of processing chamber 400 isshown according to the disclosed technology. The chamber 400 may includeany of the components as previously discussed, and may be configured tohouse a semiconductor substrate 455 in a processing region 433 of thechamber. The substrate 455 may be located on a pedestal 465 as shown.Processing chamber 400 may include two remote plasma systems (RPS) 401,402. A first RPS unit 401 may be fluidly coupled with a first access 405of the chamber 400, and may be configured to deliver a first precursorinto the chamber 400 through the first access 405. A second RPS unit 402may be fluidly coupled with a second access 410 of the chamber 400, andmay be configured to deliver a second precursor into the chamber 400through the second access 410. First and second plasma units 401, 402may be the same or different plasma systems. For example, either or bothsystems may be RF plasma systems, CCP plasma chambers, ICP plasmachambers, magnetically generated plasma systems including toroidalplasma systems, microwave plasma systems, etc., or any other system typecapable of forming a plasma or otherwise exciting and/or dissociatingmolecules therein. The system may be configured to maintain the firstand second precursors fluidly isolated from one another until they aredelivered to the process region 433 of the chamber 400. First access 405may be located near to or at the top of the processing chamber 400, andsecond access 410 may be located near or along one of the side portionsof the chamber 400.

Chamber 400 may further include a gas distribution assembly 425 withinthe chamber. The gas distribution assembly 425, which may be similar inaspects to the dual-channel showerheads as previously described, may belocated within the chamber 400 at a top portion of the processing region433, or above the processing region 433. The gas distribution assembly425 may be configured to deliver both the first and second precursorsinto the processing region 433 of the chamber 400. Although theexemplary system of FIG. 4 includes a dual-channel showerhead, it isunderstood that alternative distribution assemblies may be utilized thatmaintain first and second precursors fluidly isolated prior to theprocessing region 433. For example, a perforated plate and tubesunderneath the plate may be utilized, although other configurations mayoperate with reduced efficiency or not provide as uniform processing asthe dual-channel showerhead as described.

The gas distribution assembly 425 may comprise an upper plate 420 and alower plate 423 as previously discussed. The plates may be coupled withone another to define a volume 427 between the plates. The coupling ofthe plates may be such as to provide first fluid channels 440 throughthe upper and lower plates, and second fluid channels 445 through thelower plate 423. The formed channels may be configured to provide fluidaccess from the volume 427 through the lower plate 423, and the firstfluid channels 440 may be fluidly isolated from the volume 427 betweenthe plates and the second fluid channels 445. The volume 427 may befluidly accessible through a side of the gas distribution assembly 425,such as channel 322 as previously discussed. This portion of the gasdistribution assembly may be fluidly coupled with the second access 410in the chamber through which RPS unit 402 may deliver the secondprecursor.

The chamber may be configured to deliver the first precursor into theprocessing region 433 of the chamber from the first RPS unit 401,through the first access 405 in the chamber. The first precursor maythen be delivered through the first fluid channels 440 in the gasdistribution assembly 425. The chamber may additionally be configured toprovide the second precursor into the chamber from the second RPS 402through the second access 410 in the chamber 400. The second precursormay flow through the access 410 and into the gas distribution assembly425. The second precursor may flow through the gas distribution assemblyinto the volume 427 defined between the upper and lower plates, and thenflow down into the processing region 433 through the second fluidchannels 445 in the lower plate 423 of the gas distribution assembly425. From the coupling and configuration of the upper plate 420 andlower plate 423, the assembly may be configured to prevent the flow ofthe second precursor through the upper plate 420 of the assembly 425.This may be due to the alignment of apertures in the assembly asdiscussed previously.

The plasma cavities of the RPS units 401, 402, and any mechanicalcouplings leading to the chamber accesses 405, 410 may be made ofmaterials based on the first and second precursors selected to be flowedthrough the RPS units 401, 402. For example, in certain etchingoperations, a fluorine-containing precursor (e.g., NF3) may be flowedthrough either of the first and second RPS units, such as RPS unit 401.When a plasma is formed in the RPS unit 401, the molecules maydissociate into radical ions. If the RPS unit 401 is made of anunaltered aluminum, fluorine radicals may react with the cavity wallsforming byproducts such as aluminum fluoride. Accordingly, RPS unit 401may be formed with a first material that may be for example aluminumoxide, aluminum nitride, or another material with which the firstprecursor does not interact. The material of the RPS unit 401 may beselected based on the composition of the first precursor, and may bespecifically selected such that the precursor does not interact with thechamber components.

Similarly, the second RPS unit 402 may be made of a second material thatis selected based on the second precursor. In disclosed embodiments, thefirst and second material may be different materials. For example, if ahydrogen-containing precursor is flowed through the second RPS 402 and aplasma is formed, dissociated hydrogen radicals may interact with theplasma cavity of the RPS 402. If the chamber is similarly made ofaluminum oxide, for example, the hydrogen radicals will interact withthe oxide, and may remove the protective coating. Accordingly, RPS unit402 may be made of a second material different from the first such asaluminum, or another material with which the second precursor does notinteract. This may be extended to the gas distribution assembly as well,with the upper surface of the upper plate 420 being made of or coatedwith the same material used in the first RPS, and the bottom surface ofthe upper plate 420 and the upper surface of the lower plate 423 beingmade of or coated with the same material used in the second RPS. Suchcoatings or materials selections may improve equipment degradation overtime. Accordingly, the gas distribution assembly plates may each includemultiple plates made of one or more materials.

In operation, one or both of the RPS units 401, 402 may be used toproduce a plasma within the unit to at least partially ionize the firstand/or second precursor. In one example in which a fluorine-containingprecursor and a hydrogen-containing precursor are utilized, thehydrogen-containing precursor may be flowed through the first RPS unit401 and the fluorine-containing radical may be flowed through the secondRPS unit 402. Such a configuration may be based on the travel distancesfor the radical species. For example, the path to the processing region433 may be shorter from the first RPS unit 401. Because hydrogenradicals may recombine more quickly than fluorine radicals due to ashorter half-life, the hydrogen-containing radicals may be flowedthrough the shorter paths. Additionally, a plasma as described earliermay be formed in the region of the chamber 400 above the gasdistribution assembly 425 in order to prolong, continue, or enhance theradical species. However, other configurations disclosed may flow thehydrogen-containing precursor through the second RPS unit 402.

The RPS units 401, 402 may be operated at power levels from betweenbelow or about 10 W up to above or about 10 or 15 kW in variousembodiments. The inventors have advantageously determined that anadditional benefit of the disclosed technology is that the power andplasma profile of each RPS unit may be tuned to the particular precursorused. For example, continuing the example with a fluorine-containingprecursor and a hydrogen-containing precursor, some conventional systemsrequire that both precursors requiring dissociation be flowed throughthe same RPS unit. In addition to the potential deterioration of theplasma cavity and RPS unit as discussed above, a plasma profilebeneficial to both precursors may not be available. Continuing theexample, fluorine-containing precursors including NF3 may be processedat a relatively low level of power in the RPS unit. By operating the RPSat a power level at or below 100 W, 200 W, 400 W, up to 1000 W or more,the precursor may be dissociated to a lesser degree that does notcompletely ionize the particles, and includes independent radicalsincluding NF and NF2 species as well. Additionally, the RPS unitprocessing the hydrogen-containing precursor may be operated at a muchhigher power level as complete dissociation may be desired. Accordingly,the RPS unit may be operated between up to or above about 1000 W and upto or above about 10 kW or more. The RF frequency applied in theexemplary processing system may be low RF frequencies less than about500 kHz, high RF frequencies between about 10 MHz and about 15 MHz ormicrowave frequencies greater than or about 1 GHz in differentembodiments. As such, the first RPS unit 401 may be configured tooperate at a first power level that is selected based on the compositionof the first precursor, and the second RPS may be configured to operateat a second power level that is selected based on the composition of thesecond precursor. The two RPS units 401, 402 may be configured tooperate at power levels different from one another. Such a configurationmay require separate or decoupled power sources, among other changes.

Additional flexibility may be provided by operating one of the RPS unitsbut not the other. For example, a fluorine-containing precursor may beflowed through the first RPS unit 401 that is configured to operate at apower level that may be lower based on the precursor. Ahydrogen-containing precursor may be flowed through the second RPS unit402 in which a plasma is not formed such that the molecular precursorflows to the processing region 433. When the first and second precursorsseparately exit the gas distribution assembly 425 they may interact, andthe first precursor that has been at least partially radicalized in RPSunit 401 may ionize a portion of the second precursor, in which casepower efficiency of the system may be improved. Based on these examples,it is understood that many aspects may be reversed or changed indisclosed embodiments of the technology based on various operationalcharacteristics.

In order to better understand and appreciate the invention, reference isnow made to FIG. 5 which is a flow chart of an etch process,specifically a silicon-selective etch, according to disclosedembodiments. It is understood that the technology can similarly beutilized for deposition processes. Silicon may be amorphous,crystalline, or polycrystalline (in which case it is usually referred toas polysilicon). Prior to the first operation, a structure may be formedin a patterned substrate. The structure may possess separate exposedregions of silicon and silicon oxide. Previous deposition and formationprocesses may or may not have been performed in the same chamber. Ifperformed in a different chamber, the substrate may be transferred to asystem such as that described above.

A first precursor such as a hydrogen-containing precursor, may be flowedinto a first plasma region separate from the substrate processing regionat operation 510. The separate plasma region may be referred to as aremote plasma region herein and may be within a distinct module from theprocessing chamber or a compartment within the processing chamber.Generally speaking, a hydrogen-containing precursor may be flowed intothe first plasma region in which it is excited in a plasma, and thehydrogen-containing precursor may comprise at least one precursorselected from H2, NH3, hydrocarbons, or the like. A flow of a secondprecursor such as nitrogen trifluoride, or a differentfluorine-containing precursor, may be introduced into a second remoteplasma system at operation 520 where it is excited in a plasma. Thefirst and second plasma systems may be operated in any fashion aspreviously discussed, and in disclosed embodiments thehydrogen-containing precursor and the fluorine-containing precursor maybe flowed through the alternative RPS unit. Additionally, only one ofthe remote plasma systems may be operated in disclosed embodiments. Theflow rate of the nitrogen trifluoride may be low relative to the flowrate of the hydrogen to effect a high atomic flow ratio H:F as will bequantified shortly. Other sources of fluorine may be used to augment orreplace the nitrogen trifluoride. In general, a fluorine-containingprecursor may be flowed into the second remote plasma region and thefluorine-containing precursor comprises at least one precursor selectedfrom the group consisting of atomic fluorine, diatomic fluorine, brominetrifluoride, chlorine trifluoride, nitrogen trifluoride, hydrogenfluoride, fluorinated hydrocarbons, sulfur hexafluoride, and xenondifluoride.

The plasma effluents formed in the remote plasma regions of the firstand second precursors may then be separately flowed into and thencombined in the substrate processing region at operation 530. Thepatterned substrate may be selectively etched such that the exposedsilicon is removed at a rate at least or about seventy times greaterthan the exposed silicon oxide. The technology may involve maintenanceof a high atomic flow ratio of hydrogen (H) to fluorine (F) in orderachieve high etch selectivity of silicon. Some precursors may containboth fluorine and hydrogen, in which case the atomic flow rate of allcontributions are included when calculating the atomic flow ratiodescribed herein. The preponderance of hydrogen may help to hydrogenterminate exposed surfaces on the patterned substrate. Under theconditions described herein, hydrogen termination may be metastable ononly the silicon surfaces. Fluorine from the nitrogen trifluoride orother fluorine-containing precursor displaces the hydrogen on thesilicon surface and creates volatile residue which leaves the surfaceand carries silicon away. Due to the strong bond energies present in theother exposed materials, the fluorine may be unable to displace thehydrogen of the other hydrogen terminated surfaces (and/or is unable tocreate volatile residue to remove the other exposed material).

In one example, a gas flow ratio (H₂:NF₃) greater than or about 15:1, orin general terms, greater than or about an atomic flow ratio of between10:1, was found to achieve etch selectivity (silicon:silicon oxide orsilicon:silicon nitride) of greater than or about 70:1. The etchselectivity (silicon:silicon oxide or silicon:silicon nitride) may alsobe greater than or about 100:1, greater than or about 150:1, greaterthan or about 200:1, greater than or about 250:1 or greater than orabout 300:1 in disclosed embodiments, or between or among any of theseranges. Regions of exposed tungsten, titanium nitride, or other metalsmay also be present on the patterned substrate and may be referred to asexposed metallic regions. The etch selectivity (silicon:exposed metallicregion) may be greater than or about 100:1, greater than or about 150:1,greater than or about 200:1, greater than or about 250:1, greater thanor about 500:1, greater than or about 1000:1, greater than or about2000:1 or greater than or about 3000:1 in disclosed embodiments. Thereactive chemical species are removed from the substrate processingregion and then the substrate is removed from the processing region.

The presence of the high flow of hydrogen-containing precursor, asdescribed herein, ensures that silicon, silicon oxide and siliconnitride maintain a hydrogen-terminated surface during much of theprocessing. The fluorine-containing precursor and/or thehydrogen-containing precursor may further include one or more relativelyinert gases such as He, N₂, Ar, or the like. The inert gas can be usedto improve plasma stability and/or to carry liquid precursors to theremote plasma region. Flow rates and ratios of the different gases maybe used to control etch rates and etch selectivity. In an embodiment,the fluorine-containing gas includes NF₃ at a flow rate of between about1 sccm (standard cubic centimeters per minute) and 30 sccm, and H₂ at aflow rate of between about 500 sccm and 5,000 sccm, He at a flow rate ofbetween about 0 sccm and 3000 sccm, and Ar at a flow rate of betweenabout 0 sccm and 3000 sccm. The atomic flow ratio H:F may be kept highin disclosed embodiments to reduce or eliminate solid residue formationon silicon oxide. The formation of solid residue consumes some siliconoxide which may reduce the silicon selectivity of the etch process. Theatomic flow ratio H:F may be greater than or about twenty five (i.e.25:1), greater than or about 30:1 or greater than or about 40:1 inembodiments of the technology.

By maintaining the precursors fluidly separate, corrosion and otherinteraction with the RPS systems may be reduced or eliminated. Asdescribed above, the RPS units and distribution components including thegas distribution assembly may be made of materials selected based on theprecursors being delivered, and thus selected to prevent reactionbetween the ionized precursors and the equipment.

An ion suppressor may be used to filter ions from the plasma effluentsduring transit from the remote plasma region to the substrate processingregion in embodiments of the invention. The ion suppressor functions toreduce or eliminate ionically charged species traveling from the plasmageneration region to the substrate. Uncharged neutral and radicalspecies may pass through the openings in the ion suppressor to react atthe substrate. It should be noted that complete elimination of ionicallycharged species in the reaction region surrounding the substrate is notalways the desired goal. In many instances, ionic species are requiredto reach the substrate in order to perform the etch and/or depositionprocess. In these instances, the ion suppressor helps control theconcentration of ionic species in the reaction region at a level thatassists the process. In disclosed embodiments the upper plate of the gasdistribution assembly may include an ion suppressor.

The temperature of the substrate can be maintained at a singletemperature during processing or can be subjected to changingtemperatures. In some embodiments, the temperature of the substrate isgreater than or equal to about 350° C., 375° C., 400° C., 425° C. or450° C. In some embodiments, the temperature of the substrate issufficient to allow a titanium chloride species to react with silicon toform a titanium silicide and not react with silicon oxide or siliconnitride.

The data further show an increase in silicon etch rate as a function ofprocess pressure (for a given hydrogen:fluorine atomic ratio). However,for an atomic flow rate ratio of about 50:1 H:F, increasing the pressureabove 1 Torr may begin to reduce the selectivity. This is suspected toresult from a higher probability of combining two or morefluorine-containing effluents. The etch process may then begin to removesilicon oxide, silicon nitride, and other materials. The pressure withinthe substrate processing region may be below or about 10 Torr, below orabout 5 Torr, below or about 3 Torr, below or about 2 Torr, below orabout 1 Torr or below or about 750 mTorr in disclosed embodiments. Inorder to ensure adequate etch rate, the pressure may be above or about0.05 Torr, above or about 0.1 Torr, above or about 0.2 Torr or above orabout 0.4 Torr in embodiments of the invention.

In the preceding description, for the purposes of explanation, numerousdetails have been set forth in order to provide an understanding ofvarious embodiments of the present invention. It will be apparent to oneskilled in the art, however, that certain embodiments may be practicedwithout some of these details, or with additional details.

Having disclosed several embodiments, it will be recognized by those ofskill in the art that various modifications, alternative constructions,and equivalents may be used without departing from the spirit of thedisclosed embodiments. Additionally, a number of well-known processesand elements have not been described in order to avoid unnecessarilyobscuring the present invention. Accordingly, the above descriptionshould not be taken as limiting the scope of the invention.

Where a range of values is provided, it is understood that eachintervening value, to the smallest fraction of the unit of the lowerlimit, unless the context clearly dictates otherwise, between the upperand lower limits of that range is also specifically disclosed. Anynarrower range between any stated values or unstated intervening valuesin a stated range and any other stated or intervening value in thatstated range is encompassed. The upper and lower limits of those smallerranges may independently be included or excluded in the range, and eachrange where either, neither, or both limits are included in the smallerranges is also encompassed within the technology, subject to anyspecifically excluded limit in the stated range. Where the stated rangeincludes one or both of the limits, ranges excluding either or both ofthose included limits are also included.

FIG. 6 shows a simplified schematic of processing chamber 600 inaccordance with one or more embodiments of the disclosure. The chamber600 may include any of the components as previously discussed, and maybe configured to house a semiconductor substrate 655 in a processingregion 633 of the chamber 600. The substrate 655 may be located on apedestal 665 as shown.

A dual channel gas distribution assembly 625 is positioned within theinterior of the processing chamber 600 at a top portion of theprocessing region 633, or above the processing region 633. In theembodiment shown the processing region 633 has an upper boundary definedby the gas distribution assembly 625. The gas distribution assembly 625may be configured to deliver both the first and second precursors intothe processing region 633 of the chamber 600 so that the first andsecond precursors do not mix prior to entering the processing region633.

The gas distribution assembly 625 may comprise an upper plate 620 and alower plate 623. The plates may be coupled with one another to define avolume 627 between the plates. The coupling of the plates may be such asto provide first fluid channels 640 through the upper and lower plates,and second fluid channels 645 through the lower plate 623. The formedchannels may be configured to provide fluid access from the volumethrough the lower plate 623, and the first fluid channels 640 may befluidly isolated from the volume 627 between the plates and the secondfluid channels 645. The volume 627 may be fluidly accessible through aside of the gas distribution assembly 625, such as channel 622.

Access 405 may be located near to or at the top 671 of the processingchamber 600 and is fluidly coupled to volume 603. A gaseous species canbe flowed into volume 603 through access 605. In volume 603, the gaseousspecies can be ignited to form a plasma. The plasma is formed remotelyfrom the processing region 633 and adjacent the upper plate 620. Thefirst fluid channels 640 provide a pathway for the plasma generated inthe volume 603 to pass through the gas distribution assembly 626 intoprocessing region 633.

The plasma is formed in volume 603 by any suitable plasma generationhardware. For example, a capacitively coupled plasma (CCP) may begenerated between the top 671 and the gas distribution assembly 625. Inthe embodiment shown, a power source 690 is electrically connected tothe top 671 and the gas distribution assembly 625 to generate the plasmain volume 603. Other plasma generation systems include, but are notlimited to, inductively coupled plasma (ICP), magnetically generatedplasma systems and microwave plasma systems. While the plasma is formedin volume 603 within the processing chamber 600, the plasma generationsystems and configurations for the RPS 401, 402 are similar to theplasma generation systems and configurations of the embodiment of FIG.6.

The chamber 600 shown is configured to deliver the second precursor intothe processing region 633 of the chamber through the access 610 andsecond fluid channels 645 and passage 647 through the volume 627 of thegas distribution assembly 625. The second precursor may flow through theaccess 610 and into the gas distribution assembly 625. The secondprecursor may flow through passage 647 of the gas distribution assembly625 between the upper and lower plates, and then flow down into theprocessing region 633 through the second fluid channels 645 in the lowerplate 623 of the gas distribution assembly 625. From the coupling andconfiguration of the upper plate 620 and lower plate 623, the assemblymay be configured to prevent the flow of the second precursor throughthe upper plate 620 of the assembly 625. This may be due to thealignment of apertures in the assembly.

In some embodiments of the processing method, a first precursor isflowed into a volume 603 which is bounded by a top 671 of the processingchamber and the upper plate 620 of the gas distribution assembly 625.The first precursor is energized in the volume 603 and allowed to flowthrough first fluid channels 640 in the gas distribution assembly 625 toprocessing region 633. As used in this regard, “energized” means thatone or more of ions or radicals of the first precursor are generated inthe volume 603. In some embodiments, the energized first precursor formsa plasma of the first precursor. The first precursor can be co-flowedwith one or more carrier gases or other reactive gases. In someembodiments, the first precursor is co-flowed with argon as a carriergas.

A second precursor is flowed through second fluid channels 645 in thegas distribution assembly 625 into the processing region 633 and allowedto react with the energized first precursor. In some embodiments, thefirst fluid channel and the second fluid channel are isolated to preventgas phase mixing of the first precursor and the second precursor untilthe precursors are in the processing region. In some embodiments, thesecond precursor does not pass through a plasma generator so that onlythe first precursor is energized before entering the processing region633.

A substrate 655 is provided in the processing region 633 and the firstprecursor and second precursor deposit a film on the substrate 655. Insome embodiments, the substrate 655 has a first surface 692 and a secondsurface 693 that is different than the first surface 692. For example,the first surface can be a metal surface and the second surface can be adielectric, or vice versa. In some embodiments, the first surfacecomprises silicon and the second surface comprises silicon oxide. Insome embodiments, the first surface comprises silicon and the secondsurface comprises silicon nitride. In some embodiments, the firstsurface comprises silicon and the second surface comprises siliconoxynitride. In some embodiments, the first surface comprises silicon andthe second surface comprises one or more of silicon oxide or siliconnitride.

In some embodiments, the first precursor comprises hydrogen (H₂) andenergizing the first precursor produces H⁺ and H* species. In someembodiments, the hydrogen ions and radicals are formed as part of aplasma and allowed to flow through the first fluid channels into theprocessing region.

In some embodiments, the second precursor comprises a metal halide. Themetal can be any suitable metal species and the halide can be anysuitable halogen. The metal halide can be a mixture of differenthalogens or substantially the same halogen atom. In some embodiments,the metal halide comprises substantially only chlorine atoms. As used inthis regard, “substantially only” means that there is greater than orequal to about 95 atomic percent of the stated halogen species. In someembodiments, the halogen is one or more of fluorine, chlorine, bromineor iodine. In some embodiments, there are substantially no fluorineatoms; meaning that there is less than about 1% on an atomic basis ofall halogen atoms.

In one or more embodiments, the metal halide is a titanium chloride. Thetitanium chloride TiCl_(x) can be a mixture of titanium oxidation statesor substantially all the same oxidation state (i.e., >95% the sameoxidation state on an atomic basis). For example, the titanium chloridecan be a mixture of TiCl₃ and TiCl₄ species, or other species.

Referring to FIG. 7, without being bound by any particular theory ofoperation, it is believed that the titanium chloride reacts with theH⁺/H* species to deposit a titanium film on the substrate. The titaniumfilm forms on the first surface 692 and the second surface 693.Unreacted titanium chloride is believed to etch the titanium film formedon the second surface 693 to selectively deposit a titanium film on thefirst surface 692. The titanium film can form equally or unequally onthe first and second surfaces with etching resulting in selectivedeposition. In some embodiments, the metal film is formed on the firstsurface preferentially to the second surface and etching increases theselectivity. In some embodiments, the first surface 692 comprisessilicon and the second surface 693 comprises one or more of siliconoxide or silicon nitride.

The selectivity of the deposition is greater than or equal to about10:1. As used in this manner, selectivity is the amount of film formedon the first surface relative to the second surface. In someembodiments, the selectivity is greater than or equal to about 15:1,20:1, 25:1, 30:1, 35:1 or 40:1.

According to one or more embodiments, the substrate is subjected toprocessing prior to and/or after forming the layer. This processing canbe performed in the same chamber or in one or more separate processingchambers. In some embodiments, the substrate is moved from the firstchamber to a separate, second chamber for further processing. Thesubstrate can be moved directly from the first chamber to the separateprocessing chamber, or it can be moved from the first chamber to one ormore transfer chambers, and then moved to the separate processingchamber. Accordingly, the processing apparatus may comprise multiplechambers in communication with a transfer station. An apparatus of thissort may be referred to as a “cluster tool” or “clustered system,” andthe like.

Generally, a cluster tool is a modular system comprising multiplechambers which perform various functions including substratecenter-finding and orientation, annealing, annealing, deposition and/oretching. According to one or more embodiments, a cluster tool includesat least a first chamber and a central transfer chamber. The centraltransfer chamber may house a robot that can shuttle substrates betweenand among processing chambers and load lock chambers. The transferchamber is typically maintained at a vacuum condition and provides anintermediate stage for shuttling substrates from one chamber to anotherand/or to a load lock chamber positioned at a front end of the clustertool. Two well-known cluster tools which may be adapted for the presentdisclosure are the Centura® and the Endura®, both available from AppliedMaterials, Inc., of Santa Clara, Calif. However, the exact arrangementand combination of chambers may be altered for purposes of performingspecific steps of a process as described herein. Other processingchambers which may be used include, but are not limited to, cyclicallayer deposition (CLD), atomic layer deposition (ALD), chemical vapordeposition (CVD), physical vapor deposition (PVD), etch, pre-clean,chemical clean, thermal treatment such as RTP, plasma nitridation,anneal, orientation, hydroxylation and other substrate processes. Bycarrying out processes in a chamber on a cluster tool, surfacecontamination of the substrate with atmospheric impurities can beavoided without oxidation prior to depositing a subsequent film.

According to one or more embodiments, the substrate is continuouslyunder vacuum or “load lock” conditions, and is not exposed to ambientair when being moved from one chamber to the next. The transfer chambersare thus under vacuum and are “pumped down” under vacuum pressure. Inertgases may be present in the processing chambers or the transferchambers. In some embodiments, an inert gas is used as a purge gas toremove some or all of the reactants. According to one or moreembodiments, a purge gas is injected at the exit of the depositionchamber to prevent reactants from moving from the deposition chamber tothe transfer chamber and/or additional processing chamber. Thus, theflow of inert gas forms a curtain at the exit of the chamber.

The substrate can be processed in single substrate deposition chambers,where a single substrate is loaded, processed and unloaded beforeanother substrate is processed. The substrate can also be processed in acontinuous manner, similar to a conveyer system, in which multiplesubstrate are individually loaded into a first part of the chamber, movethrough the chamber and are unloaded from a second part of the chamber.The shape of the chamber and associated conveyer system can form astraight path or curved path. Additionally, the processing chamber maybe a carousel in which multiple substrates are moved about a centralaxis and are exposed to deposition, etch, annealing, cleaning, etc.processes throughout the carousel path.

During processing, the substrate can be heated or cooled. Such heatingor cooling can be accomplished by any suitable means including, but notlimited to, changing the temperature of the substrate support andflowing heated or cooled gases to the substrate surface. In someembodiments, the substrate support includes a heater/cooler which can becontrolled to change the substrate temperature conductively. In one ormore embodiments, the gases (either reactive gases or inert gases) beingemployed are heated or cooled to locally change the substratetemperature. In some embodiments, a heater/cooler is positioned withinthe chamber adjacent the substrate surface to convectively change thesubstrate temperature.

The substrate can also be stationary or rotated during processing. Arotating substrate can be rotated continuously or in discreet steps. Forexample, a substrate may be rotated throughout the entire process, orthe substrate can be rotated by a small amount between exposures todifferent reactive or purge gases. Rotating the substrate duringprocessing (either continuously or in steps) may help produce a moreuniform deposition or etch by minimizing the effect of, for example,local variability in gas flow geometries.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe disclosure. Thus, the appearances of the phrases such as “in one ormore embodiments,” “in certain embodiments,” “in one embodiment” or “inan embodiment” in various places throughout this specification are notnecessarily referring to the same embodiment of the disclosure.Furthermore, the particular features, structures, materials, orcharacteristics may be combined in any suitable manner in one or moreembodiments.

Although the disclosure herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent disclosure. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present disclosure without departing from the spiritand scope of the disclosure. Thus, it is intended that the presentdisclosure include modifications and variations that are within thescope of the appended claims and their equivalents.

What is claimed is:
 1. A processing method comprising: flowing a firstprecursor comprising H₂ into a volume in a processing chamber, thevolume bounded by a chamber top and a gas distribution assembly;energizing the first precursor in the volume to form H⁺ and H* speciesand allowing the first precursor to flow through first fluid channelsformed in the gas distribution assembly into a processing region in theprocessing chamber; flowing a second precursor comprising a metal halidecomprising titanium chloride through the gas distribution assemblythrough second fluid channels into the processing region to react thefirst precursor in the processing region; and contacting a substratewith the energized first precursor and the second precursor, thesubstrate having a first surface comprising Si and a second surfacedifferent from the first surface, the second surface comprising SiO₂ orSiN, wherein the titanium chloride and the H⁺ and H* species react todeposit a titanium film on the first surface and the second surface, andunreacted titanium chloride etches the titanium film formed on thesecond surface to selectively deposit a titanium film on the firstsurface.
 2. The processing method of claim 1, wherein the first fluidchannel and the second fluid channel isolated to prevent mixing of thefirst precursor and the second precursor until the precursors are in theprocessing region.
 3. The processing method of claim 1, wherein thesecond precursor does not pass through a plasma generator so that onlythe first precursor is energized before entering the processing region.4. The processing method of claim 1, wherein selectivity is greater thanor equal to about 10:1.
 5. The processing method of claim 1, wherein thefirst precursor is co-flowed with a carrier gas.
 6. A processing methodcomprising: positioning a substrate with a first surface comprising Siand a second surface different from the first surface in a processingregion of a processing chamber, the second surface comprising SiO₂ orSiN; flowing an energized first precursor through a dual channel gasdistribution assembly into the processing region, the energized firstprecursor comprises H⁺ and H* species; flowing a second precursorthrough the dual channel gas distribution assembly into the processingregion, the second precursor comprising a metal halide; and reacting theenergized first precursor and the second precursor in the processingregion to deposit a film on the first surface, wherein the metal halideand the H⁺ and H* species react to deposit a metal film on the firstsurface and the second surface and unreacted metal halide etches themetal film formed on the second surface to selectively deposit a metalfilm on the first surface with a selectivity greater than or equal toabout 10:1.
 7. The processing method of claim 6, wherein the energizedfirst precursor flows through first fluid channels in the gasdistribution assembly and the second precursor flows through secondfluid channel in the gas distribution assembly, the first fluid channelsisolated from the second fluid channels to prevent mixing of theenergized first precursor and the second precursor until the precursorsare in the processing region.
 8. The processing method of claim 6,wherein the second precursor is not energized before passing through thegas distribution assembly.